Patented Oct. 7, 1952 2,613,128 I

UNITED" STATES PATENT OFFICE 2,613,128 VAT DYEING COMPOSITIONS, INCLUDING A MIXTURE OF COBALT PHTHALOCYANINE DYES Fritz Baumann, Leverkus‘en-Bayerwerk, and Berthold Bienert, Leverkusen-Wiesdorf, Ger many, assignors to Farbenfabriken Bayer, Leverkusen, Germany 1 No Drawing. Application Marchll, 1949, Serial No. 81,025. In GermanyOctober 29, 1948 i 2 Claims. (01. 8--28)1 1- , ,i ' 2 The present invention relates to new composi acid etc. As. a matter of fact, besides such sub tions of matter which are useful for dyeing stituents‘ ‘as increase the hydrophilic property, textile ?bers from the vat. the cobalt phthalocyanines may also contain The phthalocyanines which are distinguished substituents which exert the contrary eiiect, pro by clear shadesand excellent fastness properties vided however, that there are sufficient hydro ‘have been used as yet only for pigmenting, ‘as philic substituents in order to accomplish at least substantive dyestuffs and as dyestuffs for lake a higher hydrophilic character than in the case making. ‘In British Patentv No. 322,169' some of cobalt phthalocyanine. All these substitution indications are given of phthalocyanines being products have generally better vatting properties suitable for the dyeing from the vat. These indi '10 than the unsubstituted cobalt phthalocyanine cations refer both to unsulphonated and sul itself. This is true with the reservation that the phonated products, speci?c mention being made number of hydrophilic groups must not be so high of the copper, nickel and iron complex. In as to render the products easily soluble in water reality, unsulphonated copper and nickel phthal as otherwise the ai?nity to the ?ber of the vatted ocyanines have no vatting properties. Sulphona 15 product will‘ be impaired. For this reason, it is tion products thereof are capable of being vatted advisable to substitute the dyestuffs with only but do not dye the fiber from the vat to any a small number of strong hydrophilic groups, material extent. Unsulphonated. as well as sul such as SOsH-groups or COOH-groups. _ phonated iron phthalocyanines are capable of Our present invention also comprises the use as vat dyes, also exhibit some affinity to the application of cobalt phthalocyanines with in ?ber, but yield unsatisfactory shades. - creased‘ hydrophilic properties in admixture with We have now found that cobalt phthalocya the unsubstituted cobalt phthalocyanine‘ or with nines are far superior to all other‘phthalocy cobalt phthalocyanines containing other sub anines as far as vatting properties are concerned. stituents. _We have found that even small Contrary to the unsubstituted copper and nickel amounts of hydrophilic cobalt phthalocyanines complex the unsubstituted cobalt phthalocy will do to convert larger amounts of non-hydro anine is capable of use as a vat dye and, on dye philic phthalocyanines with poor vatting prop ing from the vat, yields essentially clearer shades erties into a state in which they exhibit excellent than the iron complex. Furthermore, in contrast vatting properties. Such mixtures may be ob to all other phthalocyanines as far as these‘are tained in a simple manner, for instance, by start vattable at all, the vatted cobalt phthalocyanine ing on. cobalt phthalocyanine synthesis from a is distinguished by excellent stability on dyeing, preponderant amount of phthalic acid in admix from the hot vat. The property of vatting and ture with a small amount of hydrophilic substi yielding clear valuable dyeings on textiles from tuted phthalic acids. Another possibility of pre the vat is not restricted to the unsubstituted paring such dyestuff mixtures consists in subse cobalt phthalocyanine. According to our present quently introducing small amounts of hydro invention, the above properties to a larger extent philic substituents into the phthalocyanine

are .met with those substitution products of molecule. I _ cobalt phthalocyanine the hydrophilic property Among the various combinations of cobalt of which has been increased by substitution. For phthalocyanines with hydrophilic groups and accomplishing this e?ect, substituents of differ such without hydrophilic groups as described in ent kind may be used, for instance, sulphonic the foregoing paragraph, mixtures of the unsub acid groups, sulphonamide groups (the nitrogen stituted cobalt phthalocyanine with low sul of which may be mono- or disubstituted by alkyl-, phonated cobalt phthalocyanine are of the aryl- or aralkyl radicals), sulphinic acid groups, greatest importance. On the preparation of carboxylic, acid groups, carboxylic amide groups, such cobalt phthalocyanine sulphonic acids care cyano groups, hydroxy groups, alkoxy groups, must be taken that, in the ?rst line, monosul --SH groups, ~S.alkyl groups, nitro groups, phonic acids will be obtained. Such combina amino groups, or acylamino groups. These tions may be prepared either by cautiously sul groups may be introduced. into the cobalt phonating cobalt phthalocyanine or by starting phthalocyanine as usual, i. e. either subsequent on phthalocyanine synthesis from a mixture of to complex formation or in the course of prepar smaller amounts ' of sulphophthalic acid with ing the complex by starting from phthalic acids, larger amounts of phthalic acid. Combinations phthalonitriles etc. containing such substituents. thus obtained may be blended with unsulpho~ e. g. ll-sulphophthalic acid, li-methoxyphthalic ' nated cobalt phthalocyanine so as to exhibit the 2,613,128 3 4 desired degree of solubility. The best results are C. for 1 hour. After lifting and wringing out obtained from combinations of cobalt phthalo the wool is hanged in the air for 20 minutes. cyanine sulphonic acids and unsulphonated rinsed with water and treated with dilute acetic cobalt phthalocyanine in which the. cobalt acid (5 parts by volume ofzglacial acetic acid per phthalocyanine sulphonic acids are present in an 1000 parts by volume of water), rinsed and dried. amount of 15-40% by weight (calculated as Dyeings of good fastness properties are obtained. monosulphonic acid). _ Example 1 describes the preparation of a mix In these mixtures, sulphonic acid groups can be ture easily capable of being vatted of a cobalt replaced with a similar effect by alkylsulfonamide ' phthalocyanine sulphonic acid with cobalt groups. phthalocyanine: Cobalt phthalocyanine and the various hydro 1.6 parts of cobalt phthalocyanine are gradual philic substitution products mentioned above as ly added while stirring into 20 parts of 10% fum well as the combinations described in the fore— ing sulphuric acid at room temperature. The going will dye cellulose ?bers accordingto the green solution thus obtained is heated for about 4 methods usually applied to vat dyestuffs. In gen hours at 35—-38° C. until a sample which has been eral, the best aflinity is reached when dyeing from washed neutral with water begins to dissolve on the hot vat. Many cobalt phthalocyanines are heating with pyridine water. This degree of sul capable of being vatted even in a weakly alkaline phonation is ‘reached when about 2.7-2.9% of medium, for instance, in the presence of ammonia sulphur have entered the molecule of the cobalt and, therefore, may also be used for dyeing ani 20 phthalocyanine. When this point is reached sul mal ?bers from the vat. phonation isvstopped and the solution is diluted The following examples illustrate the invention below 40° C. with 36 parts of sulphuric acid of 66" without restricting it thereto, the parts and per Bé. When the solution 7 shows only a small centages being by weight if not otherwise stated. amount of free $03, 2.4 parts of cobalt phthalo Examples A-C describe various dyeing proc r cyanine are added below 25° C. and, as soon as esses whereas Examples ‘1-22 refer to the prep dissolution is completed, the whole is stirred into aration of various dyestuffs to be used for such about 400 parts of ice water. The precipitated dyeing processes. > dyestuff is ?ltered off and washed with hot water. Example A describes the vat dyeing with cobalt The product dyes cotton from olive colored vat phthalocyanine vat dyestuffs on cotton: 30 full, clear greenish-blue shades which are dis-_ 100 parts by volume of a cobalt phthalocyanine tinguished by excellent fastness to light. paste (corresponding to 1 part of the 100% dye A vat dyestu?’ of equal dyeing properties is ob stufl’) are added to 650 parts by volume of water tained by heating 20 parts of cobalt phthalo and 7 parts by volume of concentrated caustic cyanine in 150 parts of 10% fuming sulphuric soda solution (38° Bé.) at 50° C. 40 parts by vol acid at 45-48” C. for 2-3 hours until a sample ume of sodium hydrosulphite solution (1:10 dis which has been washed neutral with water can solved in water) are caused to react with the easily be vatted with sodium hydrosulphite and above mixture for 15 minutes at 50° C. 200 parts dilute caustic soda solution. If this is not the by volume, of Glauber’s salt solution (1:10 dis case, further 10-20 parts of 20% fuming sulphuric solved in water) are then added and 50 parts of 40 acid have to be added. The dyestuff is precipi cotton are dyed in the usual manner at 50“ C. for tated by stirring the solution into ice water and one hour. After lifting the cotton is squeezed oil‘ washing the precipitate with hot water. and hanged in the air for 10 minutes; it is rinsed Example 2 describes the preparation of a co in cold water, the dyeing is treated with dilute balt phthalocyanine with good vatting proper sulphuric acid (2 parts by volume per 1000 parts ties from phthalic acid anhydride and sodium 4 by volume of water) and it is rinsed once more sulphophthalate : with water. The dyeing is then washed at the A mixture of—— boil with Marseilles soap (2 parts per 1000 parts by volume of water), rinsed and dried. Full, blue 10.36 parts of phthalic acid anhydride to green, olive-green or grey shades are obtained. 2.86 parts of sodium 4-sulphophthalate Example B.—-3 parts by volume of caustic soda 50 3.74 parts of cobalt sulphate (83%) solution of 38° Bé., 20 parts by volume of a paste 2.34 parts of ammonium chloride of a cobalt phthalocyanine 1:100 (corresponding 29.00 parts of urea and to 0.2 part of the 100% dyestuff) and 8 parts by 0.34 part of ammonium molybdate volume of a sodium hydrosulphite solution (1 part is gradually added to 20 parts by volume of nitro dissolved per 10 parts by volume of water) are benzene at 180° C. and the melt is further heated added to 170 parts by volume of water of 60° C. at 180° C. for about 6 hours. About 60 parts by After 15 minutes 10 parts of cotton are dyed volume of methanol are stirred into the melt therein in the usual manner and, after hanging while hot. The dyestuif thus obtained is sucked in the air, it is proceeded as described in Example OE and washed out with methanol. By boiling A.‘ That process can be modi?ed by substituting 60 out with dilute hydrochloric acid, sucking off 3 parts by volume of caustic soda solution by 4.5 and washing with water the impurities arev're parts by volume of caustic soda solution or by moved from the dyestuif. After drying about 10.8 ' adding 40 parts by volume of Glauber’s salt so parts of a cobalt phthalocyanine are obtained lution (1 part per 10 parts of water). which, after redissolving from sulphuric acid Example C describes the process of a vat dye 65 ing on wool: monohydrate, dyes cotton from olive colored ,vat full, clear, blue shades of excellent fastness .to 0.2 part of a cobalt phthalocyanine easily ca light. pable of being vatted (for instance the dyestuff obtained according to Example 22) is vatted by Example 3.——A mixture of— means of 2 parts by volume of concentrated am 4.44 parts of phthalic acid anhydride monia (25%) and 0.75 part of sodium hydro 2.26 parts of phthalimide-4-sulphonamide sulphite in 120 parts by volume of water at about 1.55 parts of cobalt sulphate (83%) 75° C. The vat is then ?lled up to 500 parts by 1.18 parts of ammonium chloride volume by adding water. 10 parts of wool are 14.5 parts of urea and dyed in this liquor in the usual manner at 51-52“ 0.18 part of ammonium molybdate aeiaiae 5 isgra'dually added to. 14.5. partsoi‘volume oi. tri Example 8 describes the. preparation. of a, dye chlorobenzene and the melt is further heated at‘ stuff with good vatting properties from cobalt 180° C; ior 5-6 hours. On processing as: de~ phthalocyanine and phthalic acid anhydride:. scribed in Example 2 a cobalt. phthalocyanine A mixture of-— i with good vatting properties is obtained which dyes cotton full, very clear, blue shades of excel 1 part of cobalt phthalocyanine. . lent fastness to light. The color of the. vat. is 2 parts of water-free aluminum. chloride and‘ 10 parts of. phthalic acid anhydride olive. ‘ Example 4.-,-A mixture 015- is: heated up to 210° C. for- about 45 minutes 11.1 parts of phthalic“ acid anhydride » until the reaction'product exhibits good vatting 6.1 parts of phthalimideée-sulphomethylamide properties. 4.7 parts of cobalt sulphate (83%) ' The working. up of- the mixture can be? per-' 2.5 parts of ammonium chloride formed either in an acid or in an alkaline me 24.0 parts of urea and ~ dium. The dyestufl dyes cotton from the vat 0.4 part of ammonium. molybdat full, greenish-blue shades. ‘ Example 9.—A mixture of— is gradually added to 30 parts. by volume of tri chlorobenzene of 180° C‘. and the melt is further 8.5 parts of 4-bromophthalic acid anhydride heated at 180° C. for about 6' hours. On pro 3.05 parts of phthalimide-4-s,ulphomethylamide ceeding as described in Example 2 a cobalt 20 2.35parts- of cobalt sulphate (83%) , phthalocyanine is obtained which after pasting 1.25 parts of ammonium chloride from a mixture of sulphuric acid monohydrate 12.00 parts of urea. and and chlorosulphonic acid (5:1) , dyes cotton from 0.2 part of ammonium molybdate yellow~olive colored ‘vat full, blue shades of good fastness to water and excellent fastness to light. is gradually added while stirring to 15 parts by Example 5 .--A mixture of- volume of trichlorobenzene of 180° C. and the melt is further heated at 180° C. for about 6 8.88 parts of phthalic acid anhydride ' hours. ' 5.08 parts of phthalic acid-4-sulphodimethy - On proceeding as described in Example 2, a amide cobalt phthalocyanine is obtained which after 3.74 parts of cobaltsulphate (83%) pasting dyes cotton from olive-colored vat full. 2.34 parts of ammonium chloride greenish shades. . } 29.00 parts of urea and Example 10.—If‘ phthalimide-4-sulphomethyl 0.34 part of ammonium molybdate amide (of. Example 3) is replacedby an equiva‘ is gradually added to 20 parts by volume of nitro- : lent amount of 4-nitrophthalic acid there is ob benzene’ of 180° C. and the melt is further heated tained a. dyestu?' which dyes. cotton. from the at 180° C. for about 6 hours. > ‘ vat full, greenish-blue shades of good fastness to On proceeding as described in Example 2 a co water and very good fastness to light. balt phthalocyanine is obtained which, after Example 11.-—A mixture of— pasting from a mixture of sulphuric acid mono 16.9 parts of 4-nitrophthalic acid hydrate and chlorosulphonic acid (.5 : 1), dyes cot-' 3.1 parts of cobalt sulphate (83%) ton .from yellow-olive colored vat full, greenish 2.35 parts of ammonium chloride blue shades of excellent fastness. to light and 29.0 parts of urea and good fastness to water. 0.35 part of ammonium molybdate Example 6 describes the preparation. of a dye‘- . stuff with good vatting properties from cobalt is gradually addedv while stirring to 29 parts by phthalocyanine and phosgenei volume of trichlorobenzene at 180° C. and the 10'_parts of cobalt phthalocyanine are added at melt is further heated at 180° C. for 6-7 hours. l20-‘-130°'C. to 100 parts of amixture of aluminum On proceeding as described in Example 2 there chloride and sodium chloride (7:1). Phosgene is 50 is obtained 4.4’.4".4"'-tetranitro—cobalt phthalo introduced at 150-155” C. As soonas a sample of oyanine in a good yield which. dyes cotton from the mix is capable of being readily vatted but not yellow-colored vat very full, olive-green shades, yet soluble in dilute caustic soda solution or only the nitro groupsbeing converted thereby into slightly soluble, the reaction is stopped and the amino groups. The dyeings which are distin dyestu? is isolated as usual. The dyestuil may ' guished by very good fastness to light can ‘be 'di either directly be used for vat dyeing or, after azotized' on the ?ber and can be reacted in the dryingr and pasting from sulphuric. acid, in the usual ‘way with coupling components, very full, presence of'the same amount of cobalt phthalo olive-green to dark green dyeings of very good cyanine.v In the latter case, somewhat redder and fastness to light and excellent fastness to water fuller shades are obtained. (ii being obtained thereby. Example 7 .—A mixture of-— Example 12.-—A. mixture of— 5.55‘ parts of phthalic acid anhydride 6.00 parts of 4-acetylamino phthalic acid " 0.53 part of trimellitic acid 1.26 parts of cobalt sulphate (83%) 1.87 parts of cobalt sulphate (83%) 0.78 part of ammonium chloride 1.177 parts of ammonium chloride 9.8 parts of urea and ‘ ' 14.5 parts of urea and 0.11 part of ammonium molybdate 0.17 part of ammonium molybdate is. gradually added while. stirring to 18 parts by is gradually added to 14 parts by volume of nitro- ‘I volume of nitrobenzene at 180° C‘. and the melt benzene of 180° C. The melt is further heated at , is further heated while. stirring at 180°‘ C. for 180° C. for 6 hours while stirring and it is pro 6- hours. On proceeding as described‘ in Example ceeded as described in Example 2. The dyestuil _ 2 a cobalt phthalocyanine is obtained which, thus obtained dyes cotton from olive-colored vat after pasting. dyes cotton from olive-green col full, clear, blue shades of good flastness to water ored vat bluish-green shades of excellent fast and excellent fastness to light. ness: to light. 2,613,128 7v Example 13.—A mixture of acid, 4.4 ' .4' ' .4’ ’ ' -tetranitro-cobalt phthalocyanine is obtained. 4.4'.4".4"' - tetramercapto - cobalt 7.36 parts of 4-methoxyphthalic acid phthalocyanine obtainable therefrom dyes cotton 1.87 parts of cobalt sulphate (83%) from olive colored vat greyish-green shades 1.17 parts of ammonium chloride which, on aftertreating with bichromate in acetic 0.17 part of ammonium molybdate and acid, turn fully, grey, the fastness to water-being 14.5 parts of urea very good. is gradually added while stirring to 15 parts by Example 19.-—A mixture of volume of trichlorobenzene at 180° C. There 4.84 parts of diphenyl-3.4-dicarboxylic acid upon, it is proceeded as described in Example 2. 10 4.80 parts of phthalimide-4-sulphomethylamide 4.4’ .4’ ' .4’ ’ ’ -tetramethoxy cobalt phthalocya 1.84 parts of cobalt sulphate (83%) nine thus obtained dyes cotton from yellow-olive 0.98 part of ammonium chloride colored vat full, clear turquoise blue shades of 9.44 parts of urea and excellent fastness to light and very good fastness 0.16 part of ammonium molybdate to water. 15 Example 14 describes the preparation of a dye is introduced while stirring into 12 parts by stuif with good vatting properties from cobalt volume of trichlorobenzene at 180° C. and it is phthalocyanine and sulphur chloride: proceeded as described in Example 2. The cobalt ’ Starting at 50° C‘., 4 parts of cobalt phthalo dyestuif thus obtained dyes, after pasting from cyanine are added to a mixture of 12 parts of ethyl sulphuric acid, cotton from yellow-olive water-free aluminum chloride and 24 parts of colored vat full, greenish-blue shades. sulphur chloride, the temperature being raised Example 20.—A mixture of thereby to 60° C. Temperature is kept at 60° C. 3.68 parts of 4-methoxyphthalic acid . until a sample treated with sodium hydrosulphite 4.84 parts of diphenyl-3.4-dicarboxylic acid and dilute caustic soda solution yields a clear, 1.87 parts of cobalt sulphate (83%) olive-brown vat, this stage being achieved after 1.17 parts of ammonium chloride about 3 hours. The greenish-blue vat dyestuff 14.5 parts of urea and can be separated, for instance, by introducing the 0.17 part of ammonium molybdate reaction mixture into dilute hydrochloric acid, sucking off and afterwashing with Water. 30 is introduced while stirring into 15 parts by For further puri?cation the paste of the crude volume of trichlorobenzene at 180° C. and the dyestu? is extracted with sodium sulphide solu melt is further heated while stirring at 180° C. tion a small amount of a greenish-blue dyestuff for 5-6 hours. On proceeding as described in being dissolved thereby besides sulphur. The in Example 2 a cobalt phthalocyanine is obtained soluble blue dyestuff is ?ltered off, washed with which, after pasting from ethyl sulphuric acid, water and dried, and can directly be used for dye dyes cotton from yellow-olive colored vat clear, ing from the 'vat. full, greenish-blue shades of good fastness to water and excellent fastness to light. Example 15.-—A mixture of- Example 21 .—-A mixture of 13.32 parts of phthalic acid anhydride 40 49.0 parts of benzophenone 6.33 parts of 4-nitrophthalic acid 4.53 parts of anthraquinone-Z"-carboyl-4'-ami 5.6 parts of cobalt sulphate (83%) no - 3.4 - dicyanodiphenyl (prepared from 4' 3.51 parts of ammonium chloride amino - 3.4 - dicyanodiphenyl and anthraqui 43.5 parts of urea and none-2-carboxylic acid chloride) 0.51 part of ammonium molybdate 3.84 parts of phthalodinitrile and is added while stirring to 44 parts by volume of 1.62 parts of dehydrated cobalt chloride nitrobenzene at 180° C. and the whole is further is heated after adding a small amount of pyridine heated while stirring at 180° C. for 5-6 hours. at 240-245° C. for about 3-4 hours. After cooling On proceeding as described in Example 2, 4 down to about 80-90° C. the melt is diluted with mononitro-cobalt phthalocyanine is obtained 98 parts by volume of methanol and the sep which, in the usual way, is converted on reduction arated dyestuff is sucked 011. By washing with with sodium sulphide into 4-mono-amino cobalt methanol, boiling out with dilute hydrochloric phthalocyanine and, at last, into 4-mono-mer acid and boiling out With o-dichlorobenzene the capto-cobalt phthalocyanine by diazotizing and dyestu? is obtained in a pure state. vThe dyestu? treating the diazonium compound with potassium dyes cotton from yellow-brown colored vat clear, thiocyanate and saponifying. 4-monomercapto blue-green shades of good fastness to water. cobalt phthalocyanine dyes cotton from yellow Example 22 describes the preparation of a olive colored vat full, green to blue shades of ex dyestuff especially suitable for W001 vat dyeing. cellent fastness to light. - A mixture of Example 16.—On processing according to Ex 60 ample 15 starting, however, from 8.88 parts of 22 parts of urea phthalic acid anhydride and 12.66 parts of 4 18 parts of the condensation product of 4-amino nitrophthalic acid, 4.4-dimercapto cobalt phthalo phthalimide and betaindichloride cyanine is obtained which dyes cotton from the 2.8 parts of cobalt sulphate (83%) vat full, blue to green shades. 65 1.8 parts of ammonium chloride Example 17.—On processing according to Ex 0.25 part of ammonium molybdate and ample 15 starting, however, from 4.44 parts of 2.2 parts of benzamide phthalic acid anhydride and 18.99 parts of 4' is introduced at 180° C. into a stirring vessel and nitrophthalic acid, 4.4’.4”-trimercapto cobalt 70 the melt is stirred at 180-185° C. for 2-3 hours. phthalocyanine is obtained which dyes cotton The melt being still in a warm condition is diluted from yellow-olive colored vat bright, full, bluish with 440 parts by volume of water, acidi?ed with green shades of excellent fastness to light. hydrochloric acid and the dyestuff thus obtained Example 18.—On'processing according to Ex is salted out by adding 880 parts by volume of ample 15 leaving out, however, phthalic acid an common salt solution. The dyestuff can be puri hydride and using 25.32 parts of 4-nitrophthalic ?ed by dissolving once more in dilute hydro 2,518,128 9 10 chloric acid and saiting out with common salt > REFERENCES man. and is soluble in dilute mineral acids with a The following reference-'5, are of. record in the bh?h'frfene c a m: °°1°1'- , file of this patent: ‘ ’ ’ 1. _A vat dyeing composition comprising a 5 UNITED STATES PATENTS‘ cobalt phthalocyanine free from hydrophilic Number Name Date groups, a cobalt phthalocyanine monosulphonic 2,133,340 Bienert ______Oct. 18, 1938 acid, sodium hydrosulphite, water, and caustic FOREIGN PATENTS soda. ‘ ' 2. A vat dyeing composition comprising a mix- 10 Number Country Date ture of 60-85% of a cobalt phthalocyanine free 322 169 Great Britain .... __ Nov. 18, 1929 from hydrophilic groups and of 15-40% of cobalt phthalocyanine monosulphonic acid, sodium hy drosulphite. water. and caustic soda. FRITZ BAUMANN. 15 BERTHOLD BIENERT.